WO2022034987A1 - Procédé de fabrication de pile solaire à couche mince de pérovskite - Google Patents

Procédé de fabrication de pile solaire à couche mince de pérovskite Download PDF

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WO2022034987A1
WO2022034987A1 PCT/KR2020/017505 KR2020017505W WO2022034987A1 WO 2022034987 A1 WO2022034987 A1 WO 2022034987A1 KR 2020017505 W KR2020017505 W KR 2020017505W WO 2022034987 A1 WO2022034987 A1 WO 2022034987A1
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thin film
precursor
solar cell
manufacturing
forming
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Korean (ko)
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장혁규
이소연
이규현
박찬희
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주식회사 메카로에너지
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/24—Lead compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a technology for manufacturing a perovskite solar cell, and more particularly, to a method for manufacturing a light absorption layer of a perovskite solar cell having a two-type structure using chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • a solar cell is a device that converts solar energy into electrical energy, and was first manufactured in the 1880s and is currently used as a main power source.
  • Silicon solar cells the first-generation solar cells, are lowering production costs as a strategy to increase efficiency, but the proportion of silicon substrates in production costs is still high.
  • large-scale vacuum equipment and complicated processes are one of the reasons for increasing the production cost. This can be an unfavorable requirement for solar cell operators.
  • perovskite solar cells which are non-silicon-based and classified as third-generation solar cells, are emerging.
  • Perovskite material has high electrical conductivity due to its unique ABX3 structure (A and B are cations, X is anion). Therefore, it is possible to create a solar cell with a theoretical maximum conversion efficiency of 28% using this perovskite material.
  • perovskite solar cells are mainly capable of low-temperature, non-vacuum solution processes below 100°C, they are generally manufactured using solution processes such as spin-coating and dip-coating.
  • the solution process can be applied to flexible substrates such as polyimide (PI) films, so it has many advantages.
  • PI polyimide
  • the existing solution process has a disadvantage of reducing the quality of the solar cell due to the presence of a large number of pinholes in the deposited perovskite thin film, and the lifespan of the solar cell is shortened due to the use of organic materials. there is.
  • the perovskite light absorption layer manufactured using the conventional chemical vapor deposition (CVD) method is generally composed of only MAPbI3, and in that case, the efficiency of the light absorption layer rapidly decreases with time after the solar cell is manufactured. there is a problem.
  • the present invention has been derived to solve the problems of the prior art described above, and an object of the present invention is to form a light absorption layer of a perovskite solar cell by an iodide material deposition process in order to overcome the limitations caused by the existing solution process.
  • An object of the present invention is to provide a method for manufacturing a perovskite thin film solar cell having a two-type structure.
  • a method for manufacturing a perovskite thin film solar cell of two types according to an aspect of the present invention for solving the above technical problem is a method of manufacturing a perovskite thin film solar cell using chemical vapor deposition (CVD), , forming a Pb-I-Br thin film on a substrate in a CVD atmosphere, supplying MAI and MABr in a vapor state on the Pb-I-Br thin film, and perovskite through heat treatment after the supplying step and forming a MAPb(I x , Br 1-x ) 3 (0 ⁇ x ⁇ 1) thin film having the structure.
  • CVD chemical vapor deposition
  • the step of forming the Pb-I-Br thin film is, as a Pb precursor, red chloride, red fluoride, tetraethyl red, red acetate (lead acetate), Any one or more selected from red oxide, red sulfide, red telluride, red selenide, and red acetylacetonate may be used.
  • the step of forming the Pb-I-Br thin film comprises Iodine, 6-iodo-1-hexyne, tert-butyl iodine as I precursors. Any one or more selected from tertiary-butyl iodide, iso-propyl iodide, and ethyl iodide may be used.
  • the step of forming the Pb-I-Br thin film is, as a Br precursor, benzyl bromide (Benzyl bromide), 4- (trifluoromethyl) benzyl bromide [4- (Trifluoromethyl) benzyl bromide], bromomethane (Bromomethane), bromoethane, 2-bromobutane, 1-bromopropane, 2-bromopropane, 1-bromo-2 -Methylpropane (1-Bromo-2methylpropane), 2-bromo-2-methylpropane (2-Bromo-2methylpropane), bromocyclohexane (Bromocyclohexane), any one or more selected from bromocyclopentane (Bromocyclopantane) can be used
  • the Pb precursor, the I precursor, and the Br precursor may be simultaneously supplied into the reaction chamber.
  • the Pb precursor or the canister temperature atmosphere of the I precursor may be maintained at room temperature to 150°C.
  • the canister temperature atmosphere of the Br precursor may be maintained at -50°C to 50°C.
  • the forming of the Pb-I-Br thin film may include maintaining a temperature atmosphere of a precursor supply line for supplying the Pb precursor, the I precursor, or the Br precursor at room temperature to 200°C.
  • the temperature atmosphere of the substrate on which the Pb precursor, the I precursor, or the Br precursor is deposited may be maintained at 50° C. to 300° C.
  • the forming of the Pb-I-Br thin film includes argon (Ar), helium (He), hydrogen (H 2 ) when the Pb precursor, the I precursor, or the Br precursor is supplied into the reaction chamber. ) and nitrogen (N 2 ) Any one or a mixture thereof may be used as a carrier gas.
  • the pressure atmosphere in the reaction chamber may be maintained at 1 mTorr to 100 Torr.
  • forming the Pb-I-Br thin film may use plasma to increase the deposition rate and quality of the thin film.
  • the temperature atmosphere of the supply line may be maintained at room temperature to 200° C. in order to supply MAI and MABr in a vapor state into the reaction chamber.
  • the temperature atmosphere of the substrate to which MAI and MABr are supplied may be maintained at room temperature to 250°C.
  • the step of forming the MAPb(I x , Br 1-x ) 3 (0 ⁇ x ⁇ 1) thin film includes the MAPb(I x , Br 1-x ) 3 deposited through the supplying step.
  • the thin film can be heat-treated at a temperature of 100 to 300 °C.
  • the step of forming the MAPb(I x , Br 1-x ) 3 (0 ⁇ x ⁇ 1) thin film is, in the vacuum, argon (Ar), nitrogen (N 2 ), hydrogen (H 2 ) , it may be heat-treated in a gas atmosphere of at least one of helium (He).
  • the characteristics of the solar cell can be improved by suppressing defects such as pin-holes caused by the non-vacuum solution process.
  • FIG. 1 is a schematic diagram showing a process flow of a method for manufacturing a perovskite thin film solar cell having a two-type structure according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram illustrating a chemical vapor deposition (CVD) chamber (hereinafter referred to as a reaction chamber for short) implementing the manufacturing method of FIG. 1 .
  • CVD chemical vapor deposition
  • FIG. 3 is a schematic view showing a perovskite thin film solar cell having a two-type structure manufactured by the manufacturing method of FIG. 1 .
  • FIG. 4 is a graph measuring the energy conversion efficiency of the MAPb((I x , Br 1-x ) 3 (0 ⁇ x ⁇ 1) thin film prepared by the method of FIG. 1 .
  • FIG. 5 is an exemplary view for explaining a manufacturing process of a hole transport layer in a method for manufacturing a perovskite thin film solar cell having a two-type structure according to another embodiment of the present invention.
  • FIG. 6 is an exemplary view for explaining a manufacturing process of a hole transport layer in a method for manufacturing a perovskite thin film solar cell having a two-type structure according to another embodiment of the present invention.
  • FIG. 7A is a scanning electron microscope photograph of the semiconductor surface of the copper iodide hole transport layer manufactured through the manufacturing process of FIG. 5 .
  • FIG. 7B is a field emission scanning electron microscope photograph of a cross section of a copper iodide hole transport layer manufactured through the manufacturing process of FIG. 5 .
  • a method for manufacturing a perovskite thin film solar cell having a two-type structure is a method for manufacturing a perovskite thin film solar cell using a chemical vapor deposition (CVD) method, and is a method for manufacturing a perovskite thin film solar cell on a substrate in a CVD atmosphere.
  • CVD chemical vapor deposition
  • FIG. 1 is a schematic diagram showing a process flow of a method for manufacturing a perovskite thin film solar cell having a two-type structure according to an embodiment of the present invention.
  • the method for manufacturing a perovskite thin film solar cell having a two-type structure is a method for manufacturing a perovskite thin film solar cell using chemical vapor deposition (CVD), as shown in FIG.
  • CVD chemical vapor deposition
  • electron transfer is first performed on a substrate 10 on which a transparent conductive oxide (TCO) thin film 20 made of a material such as TiO 2 or FTO is deposited in a chemical vapor deposition (CVD) atmosphere in a reaction chamber.
  • An electron transporting layer (ETL) 30 is formed.
  • a Pb-I-Br thin film 40 is deposited on the ETL 30 in a CVD atmosphere in the reaction chamber.
  • red chloride, red fluoride, tetraethylead, red acetate, and red oxide are used as a Pb precursor.
  • red sulfide (lead sulfide), red telluride (lead telluride), red selenide (lead selenide), any one or more selected from red acetylacetonate (lead acetylacetonate) may be used as a Pb precursor.
  • iodine, 6-iodo-1-hexyne, tertiary-butyl iodide (tertiary) as I precursors -Butyl iodide), isopropyl iodide (Iso-propyl iodide), and any one or more selected from ethyl iodide (Ethyl iodide) may be used.
  • benzyl bromide 4-(trifluoromethyl)benzyl bromide [4-(Trifluoromethyl)benzyl bromide], bromomethane, Bromoethane, 2-bromobutane, 1-bromopropane, 2-bromopropane, 1-bromo-2-methylpropane ( One or more selected from 1-Bromo-2methylpropane), 2-bromo-2-methylpropane (2-Bromo-2methylpropane), bromocyclohexane, and bromocyclopentane may be used.
  • the Pb precursor, the I precursor, and the Br precursor may be set or operated to simultaneously supply the reaction chamber.
  • the Pb precursor or the canister temperature atmosphere of the I precursor may be maintained at room temperature to 150 °C.
  • the canister temperature atmosphere of the Br precursor may be maintained at -50°C to 50°C.
  • the temperature atmosphere of the precursor supply line for supplying the Pb precursor, the I precursor, or the Br precursor may be maintained at room temperature to 200°C.
  • the temperature atmosphere of the substrate on which the Pb precursor, the I precursor, or the Br precursor is deposited may be maintained at 50° C. to 300° C.
  • the Pb precursor, the I precursor, or the Br precursor when supplied into the reaction chamber, argon (Ar), helium (He), hydrogen (H 2 ) and nitrogen (N 2 ) Any one or a mixture thereof may be used as the carrier gas.
  • the pressure atmosphere in the reaction chamber may be maintained at 1 mTorr to 100 Torr.
  • plasma may be used to increase the deposition rate and quality of the thin film.
  • MAI and MABr are supplied in a vapor state on the Pb-I-Br thin film 40 .
  • the temperature atmosphere of the supply line may be maintained at room temperature to 200° C. in order to supply MAI and MABr in a vapor state into the reaction chamber.
  • the temperature atmosphere of the substrate to which MAI and MABr are supplied may be maintained at room temperature to 250°C.
  • a MAPb(I x , Br 1-x ) 3 (0 ⁇ x ⁇ 1) thin film having a perovskite structure is deposited through heat treatment.
  • the step of forming the MAPb(I x , Br 1-x ) 3 (0 ⁇ x ⁇ 1) thin film is 100 to 300 of the MAPb(I x , Br 1-x ) 3 thin film deposited through the supplying step. It can be heat-treated at a temperature of °C.
  • the step of forming the MAPb (I x , Br 1-x ) 3 (0 ⁇ x ⁇ 1) thin film is, in the vacuum, argon (Ar), nitrogen (N 2 ), hydrogen (H 2 ), helium (He ) may be heat-treated in one or more gas atmospheres.
  • FIG. 2 is a schematic diagram illustrating a chemical vapor deposition (CVD) chamber (hereinafter referred to as a reaction chamber for short) implementing the manufacturing method of FIG. 1 .
  • 3 is a schematic view showing a perovskite thin film solar cell having a two-type structure manufactured by the manufacturing method of FIG. 1 .
  • a chemical vapor deposition (CVD) apparatus for implementing a method for manufacturing a perovskite thin film solar cell having a two-type structure includes a reaction chamber 200 and vacuums the inside of the reaction chamber 200 . state can be maintained.
  • a substrate chuck 130 on which a substrate can be mounted may be provided at a lower portion of the inside of the reaction chamber 200 .
  • the substrate may be loaded into the chamber through a gate provided at one side of the chamber, and may be fixed by being placed on the substrate chuck 130 .
  • the gate may be sealed, and the pressure inside the chamber may be reduced by a pressure adjusting means coupled to the chamber for a vacuum atmosphere inside the chamber.
  • the pressure inside the chamber is preferably maintained at about 0.01 mtorr to atmospheric pressure.
  • a showerhead to which a process gas may be supplied may be provided at an upper portion of the chamber.
  • the showerhead may have a plurality of fine holes having a diameter of 0.5 mm to 1 mm.
  • Process gases such as a Pb precursor, an I precursor, a Br precursor, and MA, may be spatially and uniformly supplied on the substrate through the showerhead.
  • the showerhead is connected to one or more canisters disposed outside through a supply line, and may receive a process gas from each canister.
  • a heater for controlling the temperature atmosphere of the substrate chuck, the canister, and the supply line and a temperature control means coupled to the heater are provided, and the timing of supplying the precursor into the reaction chamber is controlled by being coupled to the canister or the supply line. It may be provided with a supply control means.
  • the reaction chamber 200 is a Pb-I-Br thin film using a chemical vapor deposition method on a substrate placed on a substrate chuck or support 130 for manufacturing a solar cell light absorption layer under a vacuum atmosphere 210 inside.
  • MAPb(1x, Br1-x)3 (0 ⁇ x ⁇ 1) thin film is formed through heat treatment at a specific temperature, pressure or gas atmosphere by supplying MAI and MABr on the Pb-I-Br thin film.
  • MA represents a methylammonium ion (CH 3 NH 3 ).
  • a Pb precursor in the reaction chamber 100 by a chemical vapor deposition (CVD) method. and I precursor and Br precursor are supplied simultaneously or sequentially to form Pb-I-Br thin film 40 on ETL 30 including TiO 2 thin film, etc., and MAI on Pb-I-Br thin film 40
  • a MAPb (I x , Br 1-x ) (0 ⁇ x ⁇ 1) thin film 40p having a perovskite structure of two types through heat treatment after supplying MABr.
  • FIG. 4 is a graph measuring the energy conversion efficiency of the MAPb((Ix, Br1-x)3 (0 ⁇ x ⁇ 1) thin film manufactured by the method of FIG. 1 .
  • the double-structured perovskite thin film solar cell manufactured by the CVD method of this example exhibited an energy conversion efficiency of 15.2%.
  • the fill factor corresponds to a value obtained by dividing the power of the maximum power point by the product of the open-circuit voltage (V OC ) and the short-circuit current (I SC ), and was calculated as 62.1%.
  • the amount of heat (J SC ) at the maximum power point was 25.9 mA/cm 2 .
  • the size of the specimen used in this example was 2 mm x 4 mm.
  • a copper iodide thin film may be deposited on the perovskite having a two-type structure forming a light absorption layer.
  • the copper iodide thin film consists of a sequential process of depositing a copper (Cu) or iodine (I) precursor compound by sequentially supplying it into the chamber, or simultaneously supplying and depositing a copper (Cu) or iodine (I) precursor compound into the chamber at the same time It can be formed by applying the manufacturing process of either of the two methods of the process.
  • FIG. 5 is an exemplary view for explaining a manufacturing process of a hole transport layer in a method for manufacturing a perovskite thin film solar cell having a two-type structure according to another embodiment of the present invention.
  • the hole transport layer of the perovskite thin film solar cell according to the present embodiment may be formed through a sequential process of sequentially supplying a Cu precursor and an I precursor into a reaction chamber.
  • the hole transport layer is formed on the light absorption layer of the perovskite (perovskite) of the two types described above.
  • any one or more of Cu(hfac) 2 , Cu(hfac)VTMS, Cu(sBu-Me-amd) 2 , and CpCuPEt 3 may include
  • the temperature of the canister containing the Cu precursor compound source is set and maintained in the range of 0 to 80°C. And the temperature of the supply line leading from the canister to the chamber is set to 30 to 100 °C.
  • the carrier gas for the copper deposition process may be He, N 2 , and Ar, and the flow rate is controlled in the range of 100 sccm (Standard Cubic Centimeter per Minute, cm3/min) to 7,000 sccm.
  • the temperature of the susceptor in the chamber for the copper deposition process may be set to 50°C to 500°C.
  • the showerhead temperature can be adjusted, and the setting is maintained in the range of 30 to 100 °C.
  • the process pressure in the reaction chamber is adjusted in the range of 100 mTorr to 10 Torr, and the plasma may be additionally controlled and maintained at 100 to 5,000W.
  • I precursor compounds used in the iodine deposition process performed after the copper deposition process according to the sequential process, (CH 3 CH 2 )I, I 2 , ICl, 6-Iodo-1-Hexyne, Tert- Butyl iodide, (CH 3 ) 2 Any one or more of CHI may be selected and used.
  • I precursor can also be used as a solution, and the solvent includes any one or more selected from 2-methoxyethanol, 2-propanol, THF, and ethanol, and the concentration thereof may be 0.01 to 2.0M.
  • the temperature of the canister containing the iodine (I) precursor compound source is set and maintained in a temperature range of -30°C to 50°C. At this time, the temperature of the supply line leading from the canister to the chamber is set and maintained in a temperature range of 30 to 100°C.
  • Carrier gas for the iodine deposition process He, N 2 , Ar may be used alone or mixed with any one or more, the flow rate can be adjusted in the range of 100 sccm to 7,000 sccm.
  • the susceptor temperature in the chamber for the iodine deposition process may be set to 50°C to 500°C.
  • the process pressure may be controlled and maintained at 100 mTorr to 10 Torr, and additionally, the plasma may be controlled and maintained at 100 to 5,000W.
  • FIG. 6 is an exemplary view for explaining a manufacturing process of a hole transport layer in a method for manufacturing a perovskite thin film solar cell having a two-type structure according to another embodiment of the present invention.
  • the hole transport layer of the perovskite thin film solar cell according to the present embodiment may be formed through a simultaneous process.
  • the susceptor temperature in the chamber the showerhead temperature, the waiting time in the chamber, the process pressure, and the process time follow the copper deposition process conditions.
  • the organometallic (MO) source (Cu+I) used in the simultaneous process is a copper (Cu) precursor compound, Cu(hfac) 2 , Cu(hfac)VTMS, Cu(sBu-Me-amd) 2 , CpCuPEt 3 Copper containing at least one and any one or more of (CH 3 CH 2 )I, I 2 , ICl, 6-Iodo-1-Hexyne, Tert-Butyl iodide, (CH 3 ) 2 CHI as a precursor compound of at least one and iodine (I) (Cu) and iodine (I) precursor compound (CuI) is mixed and used.
  • the temperature of the canister containing the organic metal (MO) source (CuI) used in the simultaneous process is set and maintained in the range of 0 to 80 degrees.
  • the temperature of the supply line leading from the canister to the chamber is set to 30 to 100 degrees
  • the carrier gas is He, N 2 , Ar can be used, and the flow rate is adjusted in the range of 100 sccm to 7,000 sccm, and the susceptor temperature in the chamber may be set to 50 degrees to 500 degrees.
  • the temperature of the showerhead can be adjusted, and the setting can be maintained in the range of 30 to 100 degrees.
  • the process pressure is set and controlled in the range of 100 mTorr to 10 Torr, and additionally, the plasma can be used by controlling and maintaining it at 100 to 5,000 W.
  • FIG. 7A is a field emission scanning electron microscope photograph of the semiconductor surface of the copper iodide hole transport layer manufactured through the manufacturing process of FIG. 5 .
  • FIG. 7B is a field emission scanning electron microscope photograph of a cross section of a copper iodide hole transport layer manufactured through the manufacturing process of FIG. 5 .
  • the copper iodide hole transport layer manufactured by the method for manufacturing the hole transport layer according to this embodiment has a thickness of 10 to 100 nm, and transmittance is 50 to 90% in the 400 to 1100 nm region, and the hole It can be seen that the mobility has a characteristic measured in the range of 1 to 20 (cm 2 /Vs).

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Abstract

L'invention concerne un procédé de fabrication d'une pile solaire à couche mince de pérovskite, une couche d'absorption de lumière, avec deux types de structures, pour une cellule solaire de pérovskite étant fabriquée à l'aide d'un dépôt chimique en phase vapeur (CVD). Le procédé de fabrication est dirigé vers un procédé de fabrication d'une cellule solaire à couche mince de pérovskite à l'aide d'un dépôt chimique en phase vapeur (CVD), le procédé comprenant les étapes consistant à : former une couche mince de Pb-I-Br sur un substrat dans une atmosphère de CVD ; apporter du MAI et du MABr dans une phase vapeur sur la couche mince de Pb-I-Br ; et former une couche mince de MAPb(Ix, Br1-x)3(0<x<1) à structure pérovskite par traitement thermique après l'étape d'apport.
PCT/KR2020/017505 2020-08-11 2020-12-03 Procédé de fabrication de pile solaire à couche mince de pérovskite WO2022034987A1 (fr)

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KR20190034698A (ko) * 2015-07-10 2019-04-02 히 솔라, 엘.엘.씨. 페로브스카이트 물질 층 가공
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